Names | |
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IUPAC name Bis(η8-cyclooctatetraenyl)neptunium(IV) | |
Other names Neptunium cyclooctatetraenide Np(COT)2 | |
Identifiers | |
3D model (JSmol) | |
| |
| |
Properties | |
C16H16Np | |
Molar mass | 445 g·mol−1 |
Appearance | dark brown crystals as a solid, yellow in dilute solution |
insoluble, does not react with water | |
Solubility in chlorocarbons | sparingly soluble (ca. 0.5 g/L) |
Hazards | |
Occupational safety and health (OHS/OSH): | |
Main hazards | radiation hazard, pyrophoric |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Neptunocene, Np(C8H8)2, is an organoneptunium compound composed of a neptunium atom sandwiched between two cyclooctatetraenide (COT2-) rings. As a solid it has a dark brown/red colour but it appears yellow when dissolved in chlorocarbons, in which it is sparingly soluble. [1] [2] [3] [4] [5] The compound is quite air-sensitive. [1] [2] [5]
It was one of the first organoneptunium compounds to be synthesised, and is a member of the actinocene family of actinide-based metallocenes. [2]
The sandwich structure of neptunocene has been determined by single crystal XRD. [4] The COT2- rings are found to be planar with 8 equivalent C–C bonds of 1.385 Å length, and sit parallel in an eclipsed conformation. The Np–COT distance (to the ring centroid) is 1.909 Å and the individual Np–C distances are 2.630 Å. [4]
Neptunocene assumes a monoclinic crystal structure (P21/n space group) which is isomorphous to uranocene and thorocene but not to plutonocene. [4]
Neptunocene was first synthesised in 1970 by reacting neptunium(IV) chloride (NpCl4) with dipotassium cyclooctatetraenide (K2(C8H8)) in diethyl ether or THF: [1]
The same reaction conditions have been routinely reproduced since then for the synthesis of the compound. [3] [4]
The three actinocenes uranocene, neptunocene, and plutonocene share virtually identical chemistry: they do not react in the presence of water or dilute base, but are very air-sensitive, quickly forming oxides. [1] [2] [3] All three are only slightly soluble (up to about 10−3 M concentrations) in aromatic or chlorinated solvents such as benzene, toluene, carbon tetrachloride or chloroform. [1] [2] [4] [5]
A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5H−
5, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride or vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.
Neptunium is a chemical element; it has symbol Np and atomic number 93. A radioactive actinide metal, neptunium is the first transuranic element. It is named after Neptune, the planet beyond Uranus in the Solar System, which uranium is named after. A neptunium atom has 93 protons and 93 electrons, of which seven are valence electrons. Neptunium metal is silvery and tarnishes when exposed to air. The element occurs in three allotropic forms and it normally exhibits five oxidation states, ranging from +3 to +7. Like all actinides, it is radioactive, poisonous, pyrophoric, and capable of accumulating in bones, which makes the handling of neptunium dangerous.
1,3,5,7-Cyclooctatetraene (COT) is an unsaturated derivative of cyclooctane, with the formula C8H8. It is also known as [8]annulene. This polyunsaturated hydrocarbon is a colorless to light yellow flammable liquid at room temperature. Because of its stoichiometric relationship to benzene, COT has been the subject of much research and some controversy.
Uranocene, U(C8H8)2, is an organouranium compound composed of a uranium atom sandwiched between two cyclooctatetraenide rings. It was one of the first organoactinide compounds to be synthesized. It is a green air-sensitive solid that dissolves in organic solvents. Uranocene, a member of the "actinocenes," a group of metallocenes incorporating elements from the actinide series. It is the most studied bis[8]annulene-metal system, although it has no known practical applications.
In organometallic chemistry, a sandwich compound is a chemical compound featuring a metal bound by haptic, covalent bonds to two arene (ring) ligands. The arenes have the formula CnHn, substituted derivatives and heterocyclic derivatives. Because the metal is usually situated between the two rings, it is said to be "sandwiched". A special class of sandwich complexes are the metallocenes.
Organoactinide chemistry is the science exploring the properties, structure, and reactivity of organoactinide compounds, which are organometallic compounds containing a carbon to actinide chemical bond.
Organouranium chemistry is the science exploring the properties, structure, and reactivity of organouranium compounds, which are organometallic compounds containing a carbon to uranium chemical bond. The field is of some importance to the nuclear industry and of theoretical interest in organometallic chemistry.
Kenneth Norman Raymond is a bioinorganic and coordination chemist. He is Chancellor's Professor of Chemistry at the University of California, Berkeley, Professor of the Graduate School, the Director of the Seaborg Center in the Chemical Sciences Division at Lawrence Berkeley National Laboratory, and the President and Chairman of Lumiphore.
Neptunium(VI) fluoride (NpF6) is the highest fluoride of neptunium, it is also one of seventeen known binary hexafluorides. It is an orange volatile crystalline solid. It is relatively hard to handle, being very corrosive, volatile and radioactive. Neptunium hexafluoride is stable in dry air but reacts vigorously with water.
In chemistry, the cyclooctatetraenide anion or cyclooctatetraenide, more precisely cyclooctatetraenediide, is an aromatic species with a formula of [C8H8]2− and abbreviated as COT2−. It is the dianion of cyclooctatetraene. Salts of the cyclooctatetraenide anion can be stable, e.g., Dipotassium cyclooctatetraenide or disodium cyclooctatetraenide. More complex coordination compounds are known as cyclooctatetraenide complexes, such as the actinocenes.
Actinocenes are a family of organoactinide compounds consisting of metallocenes containing elements from the actinide series. They typically have a sandwich structure with two dianionic cyclooctatetraenyl ligands (COT2-, which is C
8H2−
8) bound to an actinide-metal center (An) in the oxidation state IV, resulting in the general formula An(C8H8)2.
Many compounds of thorium are known: this is because thorium and uranium are the most stable and accessible actinides and are the only actinides that can be studied safely and legally in bulk in a normal laboratory. As such, they have the best-known chemistry of the actinides, along with that of plutonium, as the self-heating and radiation from them is not enough to cause radiolysis of chemical bonds as it is for the other actinides. While the later actinides from americium onwards are predominantly trivalent and behave more similarly to the corresponding lanthanides, as one would expect from periodic trends, the early actinides up to plutonium have relativistically destabilised and hence delocalised 5f and 6d electrons that participate in chemistry in a similar way to the early transition metals of group 3 through 8: thus, all their valence electrons can participate in chemical reactions, although this is not common for neptunium and plutonium.
Plutonocene, Pu(C8H8)2, is an organoplutonium compound composed of a plutonium atom sandwiched between two cyclooctatetraenide (COT2-) rings. It is a dark red, very air-sensitive solid that is sparingly soluble in toluene and chlorocarbons. Plutonocene is a member of the actinocene family of metallocenes incorporating actinide elements in the +4 oxidation state.
Neptunium(III) fluoride or neptunium trifluoride is a salt of neptunium and fluorine with the formula NpF3.
Neptunium(V) fluoride or neptunium pentafluoride is a chemical compound of neptunium and fluorine with the formula NpF5.
Neptunium (IV) oxalate is an inorganic compound, a salt of neptunium and oxalic acid with the chemical formula Np(C2O4)2. The compound is slightly soluble in water, forms crystalline hydrates—green crystals.
Protactinium compounds are compounds containing the element protactinium. These compounds usually have protactinium in the +5 oxidation state, although these compounds can also exist in the +2, +3 and +4 oxidation states.
Neptunium compounds are compounds containg the element neptunium (Np). Neptunium has five ionic oxidation states ranging from +3 to +7 when forming chemical compounds, which can be simultaneously observed in solutions. It is the heaviest actinide that can lose all its valence electrons in a stable compound. The most stable state in solution is +5, but the valence +4 is preferred in solid neptunium compounds. Neptunium metal is very reactive. Ions of neptunium are prone to hydrolysis and formation of coordination compounds.
Americium compounds are compounds containing the element americium (Am). These compounds can form in the +2, +3, and +4, although the +3 oxidation state is the most common. The +5, +6 and +7 oxidation states have also been reported.
Organothorium chemistry describes the synthesis and properties of organothorium compounds, chemical compounds containing a carbon to thorium chemical bond.